1,1-dimethyl-5,7-di-t-butylspiro[2.5]octa-4,7-dien-6-one | 17207-20-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,1-dimethyl-5,7-di-t-butylspiro[2.5]octa-4,7-dien-6-one
• 英文别名: 5,7-Di-tert-butyl-2,2-dimethyl-spiro[2.5]octa-4,7-dien-6-on；5,7-Ditert-butyl-2,2-dimethylspiro[2.5]octa-4,7-dien-6-one；5,7-ditert-butyl-2,2-dimethylspiro[2.5]octa-4,7-dien-6-one
• CAS: 17207-20-4
• 化学式: C₁₈H₂₈O
• 分子量: 260.42
• InChiKey: ZTRVFGUJAQCSDT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.8
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.72
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1,1-dimethyl-5,7-di-t-butylspiro[2.5]octa-4,7-dien-6-one 在 4,4'-二甲氧基芪 、 叠氮化四丁基铵 作用下， 以 乙腈 为溶剂， 生成 1,1-dimethyl-5,7-di-t-butylspiro[2.5]octa-4,7-dien-6-one radical anion
  参考文献：
  名称：

  环丙基羰基→酮基自由基阴离子的均烯丙基型开环。结构/反应性关系以及溶剂/抗衡剂重组对内在障碍的贡献

  摘要：

  以下通过Mathivanan，约翰斯顿，和Wayner（开发的协议J.物理学。化学。1995，99，8190-8195），环丙基几个和含有环氧乙烷基-羰基的化合物的自由基阴离子到测量的速率常数的努力产生了用激光闪光光解法测定它们的开环（k o）。将这些实验的结果与从早期电化学研究中获得的结果进行了比较，并且通过使用与逐步解离电子转移有关的Savéant理论（Acc.Chem。 RES。1993年，26，455-461）。与中性自由基的环丙基碳烯基→均烯丙基重排相比，在可比较的驱动力下，自由基阴离子环的开口略慢。速率上的小差异归因于自由基阴离子重排额外的约2 kcal / mol溶剂重组组分的贡献。认为用于这些自由基阴离子的开环的溶剂重组能很小，这是因为在进展反应物→过渡态→产物中负电荷没有明显地移动。

  DOI：

  10.1021/jo047917r

文献信息

• Utilization of 1,1-dimethyl-4,6-di-tert-butylspiro[2,5]octa-3,6-dien-5-one as a ‘hypersensitive’ probe for single electron transfer to carbonyl compounds
  作者：James M. Tanko、Larry E. Brammer

  DOI：10.1039/c39940001165

  日期：——

  The use of 1,1-dimethyl-4,6-di-tert-butylspiro[2,5]octa-3,6-dien-5-one 1 as a ‘hypersensitive’ probe for single electron transfer in the reaction of several nucleophiles (RMgX, RLi and R2CuLi) with carbonyl compounds is demonstrated.

  在几种亲核物（RMgX、RLi 和 R2CuLi）与羰基化合物的反应中，将 1,1-二甲基-4,6-二叔丁基螺[2,5]辛-3,6-二烯-5-酮 1 用作单电子转移的 "高灵敏度 "探针。
• Radical Ion Probes. 8. Direct and Indirect Electrochemistry of 5,7-Di-<i>tert</i>-butylspiro[2.5]octa-4,7-dien-6-one and Derivatives
  作者：J. Paige Phillips、Jason G. Gillmore、Phillip Schwartz、Larry E. Brammer、Daniel J. Berger、J. M. Tanko

  DOI：10.1021/ja972795o

  日期：1998.1.1

  (stable) distonic radical anion. The direct electrochemistry of these compounds is characterized by rate limiting electron transfer (with α ≈ 0.5), suggesting that while ring opening is extremely rapid, the radical anions do have a discrete lifetime (i.e., electron transfer and ring opening are not concerted). Utilizing homogeneous redox catalysis, rate constants for electron transfer between 1a, 1b,

  5,7-二叔丁基螺[2.5]octa-4,7-dien-6-one (1a), 1-methyl-5,7-di-tert-butylspiro[2.5]octa-4,7-dien-6-one (1a), 1-methyl-5,7-di-tert-butylspiro[2.5] 的直接和间接电化学结果2.5]octa-4,7-dien-6-one (1b) 和 1,1,-dimethyl-5,7-di-tert-butylspiro[2.5]octa-4,7-dien-6-one (1c ) 报道。产物分析表明，所有这些底物的还原都会导致环丙烷开环产物；开环以适度的选择性发生，导致更多取代（稳定）的异张力自由基阴离子。这些化合物的直接电化学的特点是电子转移限速（α≈0.5），这表明虽然开环非常快，但自由基阴离子确实具有离散的寿命（即电子转移和开环不协调）。利用均相氧化还原催化，1a、1b、1b
• Radical ion probes. 11. Reaction of 1,1-dimethyl-5,7-di-t-butylspiro[2.5]octa-4,7-dien-6-one with 5-hexenyl magnesium bromide
  作者：Jason G. Gillmore、James M. Tanko

  DOI：10.1016/s0040-4039(98)01975-3

  日期：1998.11

  probe for the detection of single electron transfer (SET), the reaction of1 with 5-hexenyl magnesium bromide was examined in the hopes of observing cyclization of any intermediate 5-hexenyl radicals to cyclopentylcarbinyl radicals. A polar process dominated the reaction, but in the less prevalent SET process, the 5-hexenyl → cyclopentylcarbinyl rearrangement was extensive, indicative of freely diffusing

  在一个正在进行的努力建立1,1-二甲基-5,7-二-吨叔丁基螺[2.5]辛-4,7-二烯-6-酮（1）作为用于检测单电子转移的机械探针（ （SET），检查了1与5-己烯基溴化镁的反应，以期观察到任何中间体5-己烯基自由基成环戊基羰基自由基的环化。极性过程主导了反应，但是在不太普遍的SET过程中，5-己烯基→环戊基碳烯基重排范围很广，表明顺磁性中间体可以自由扩散。
• Radical Ion Probes. 7. Behavior of a “Hypersensitive” Probe for Single Electron Transfer in Reactions <i>Not</i> Involving Electron Transfer
  作者：James M. Tanko、Larry E. Brammer

  DOI：10.1021/jo970584w

  日期：1997.8.1

  1-Methyl-5,7-di-tert-butylspiro[2.5]octa-4,7-dien-6-one (8) and 1,1-dimethyl-5,7-di-tert-butylspiro[2.5]octa-4,7-dien-6-one (1) react with thiophenoxide ion to produce cyclopropane ring-opened products. Thermodynamic considerations effectively rule out any possibility that single electron transfer is involved in theses reactions; the process PhS- + substrate --> PhS. + substrate(.-) is endothermic by over 50 kcal/mol! Nucleophilic attack occurs both at the least- and most-hindered carbons of the cyclopropyl group, and the product ratio (R(1 degrees/2 degrees) from 8 and R(1 degrees/3 degrees) from 1, where 1 degrees, 2 degrees, and 3 degrees refer to the regioisomeric phenyl sulfides formed from these substrates) is found to vary with solvent. In dipolar, aprotic solvents, nucleophilic attack occurs preferentially at the least-hindered carbon of the cyclopropyl group (R(1 degrees/2 degrees) and R(1 degrees/3 degrees) approximate to 4-5), consistent with an S(N)2 mechanism. In protic solvents, products arising from nucleophilic attack at the more-substituted carbon of the cyclopropyl group become increasingly important, consistent with the onset of a carbocationic (S(N)2(C+)) pathway. The strengths and weaknesses of 1 and 8 as probes for single electron transfer are discussed in the context of these results.
• Tanko, James M.; Brammer, Larry E.; Hervas, Manuel, Journal of the Chemical Society. Perkin transactions II, 1994, # 5, p. 1407 - 1410
  作者：Tanko, James M.、Brammer, Larry E.、Hervas, Manuel、Campos, Kevin

  DOI：——

  日期：——